PBS (Phosphate Buffer Solution) resin composition as well as preparation method and application thereof

Abstract

The invention provides a PBS (Phosphate Buffer Solution) resin composition as well as a preparation method and application thereof. The PBS resin composition comprises PBS resin, a titanium element, a phosphorus element and an antimony element, in the PBS resin composition, the weight content of a titanium element is 20 to 150ppm, the weight content of a phosphorus element is 2 to 50ppm, and the weight content of an antimony element is 1 to 100ppm; in the PBS resin composition, the weight ratio of a titanium element to a phosphorus element to an antimony element is (2-20): 1: (0.5-10). The PBS resin composition provided by the invention contains the titanium element, the phosphorus element and the antimony element, and the weight ratio of the titanium element to the phosphorus element to the antimony element is controlled within a specific range, so that the PBS resin composition has low yellowness and excellent heat resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of degradable plastics and relates to a PBS resin composition and a preparation method and application thereof. Background Art

[0002] Polybutylene succinate (PBS) is a widely used aliphatic biodegradable polyester with good biocompatibility, biodegradability, mechanical properties and processability. It is widely used in the packaging field, such as garbage bags, shopping bags, agricultural films, etc. It not only has the basic properties of packaging materials, but is also biodegradable, solving the problem of environmental pollution.

[0003] However, with the development of science and technology and the advancement of technology, the industry has put forward higher requirements on the performance of PBS resin materials, that is, to reduce the yellowness of PBS resin materials and improve the heat resistance of PBS resin materials without affecting other properties of PBS resin, thereby extending the service life of PBS resin materials and obtaining more beautiful products.

[0004] Therefore, it is desirable in the art to develop a PBS resin composition having both low yellowness and excellent heat resistance. Summary of the invention

[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide a PBS resin composition and a preparation method and application thereof. The PBS resin composition provided by the present invention has low yellowness and excellent heat resistance.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a PBS resin composition, comprising a PBS resin, a titanium element, a phosphorus element and an antimony element; in the PBS resin composition, the weight content of the titanium element is 20-150 ppm, the weight content of the phosphorus element is 2-50 ppm, and the weight content of the antimony element is 1-100 ppm; in the PBS resin composition, the weight ratio of the titanium element, the phosphorus element and the antimony element is (2-20):1:(0.5-10), wherein 2-20 can be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or a range between any of the above values; 0.5-10 can be, for example, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or a range between any of the above values.

[0008] The PBS resin composition provided by the present invention introduces titanium, phosphorus and antimony elements, and by controlling the respective contents of titanium, phosphorus and antimony elements and the weight ratio of the three elements within a specific range, the PBS resin composition has low yellowness and excellent heat resistance.

[0009] Preferably, in the PBS resin composition, the weight content of titanium element is 20-150ppm (for example, it can be 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm or the range between any of the above values), and the weight content of phosphorus element is 2-50ppm (for example, it can be 2ppm, 4ppm, 6ppm, 8ppm, 10ppm, 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, ppm, 40ppm, 45ppm, 50ppm or ranges between any of the above values), the weight content of antimony element is 1-100ppm (for example, it can be 1ppm, 2ppm, 4ppm, 6ppm, 8ppm, 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm or ranges between any of the above values), and further preferably, the weight content of titanium element is 30-130ppm, the weight content of phosphorus element is 5-22ppm, and the weight content of antimony element is 20-70ppm.

[0010] In the present invention, the weight contents of titanium, phosphorus and antimony in the PBS resin composition are tested with reference to USEPA 3052:1996 method, analyzed by ICP-OES, and measured according to the following procedure: 0.1 g of the PBS resin composition is weighed, crushed, and 5 mL of nitric acid is added to completely immerse the PBS resin composition, and then 1.0 mL of hydrogen peroxide is dropped to react for 2 minutes, sealed in a microwave digestion tank and digested at 210° C. for 3 hours, cooled to room temperature, filtered with a 0.45 μm filter membrane, and diluted to 50 mL with distilled water, and tested by ICP-OES (Spectro arcos FHS12 inductively coupled plasma emission spectrometer, AMETEK, USA).

[0011] Preferably, in the PBS resin composition, the weight ratio of titanium element, phosphorus element and antimony element is (3-15):1:(1-8), and more preferably (4-11.5):1:(2-6.5).

[0012] Preferably, the source of the phosphorus element includes a phosphorus-containing compound, and the phosphorus-containing compound includes at least one of a phosphorus acid compound, a phosphorus oxide, a phosphorus salt compound or a phosphorus ester compound.

[0013] In the present invention, the phosphorus acid compounds include but are not limited to at least one of phosphoric acid, phosphorous acid, and hypophosphorous acid; the phosphorus oxides include but are not limited to at least one of phosphorus pentoxide and phosphorus trioxide; the phosphorus salt compounds include but are not limited to at least one of orthophosphate, hydrogen phosphate, dihydrogen phosphate, phosphite, and hypophosphite; the salt compounds include sodium salts, potassium salts, etc.; the phosphorus ester compounds include but are not limited to at least one of tri-C1-C6 alkyl phosphates (such as triethyl phosphate, trimethyl phosphate, tributyl phosphate, etc.), triphenyl phosphate, tri-C1-C6 alkyl phosphite, and triphenyl phosphite.

[0014] Preferably, the source of the antimony element includes an antimony-containing compound, and the antimony-containing compound includes at least one of antimony oxide, antimony sulfide, antimony hydroxide, antimony salt compound or antimony metal compound.

[0015] In the present invention, the antimony oxide includes but is not limited to at least one of ethylene glycol antimony, antimony trioxide, and antimony pentoxide; the antimony sulfide includes but is not limited to at least one of antimony trisulfide, antimony pentasulfide, and antimony disulfide; the antimony salt compound includes but is not limited to at least one of antimony acetate, antimony triacetate, and antimony halides (such as antimony chloride, antimony bromide, antimony fluoride, antimony iodide, etc.); the antimony metal compound refers to a compound formed by antimony and other metals, such as indium antimonide, silver antimonide, etc.

[0016] Preferably, the source of the titanium element includes a titanium-containing compound, and the titanium-containing compound includes at least one of a titanium oxide, a titanium ester compound or a titanium salt compound.

[0017] In the present invention, the titanium oxide includes but is not limited to titanium dioxide; the titanium ester compound includes a compound having the general formula Ti(OR)4, wherein R is selected from any one of a straight chain or branched alkyl group of C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10), an aromatic group of C6-C10 (for example, C6, C7, C8, C9 or C10), such as n-butyl titanate and / or isopropyl titanate; the titanium salt compound includes but is not limited to at least one of a titanate (such as barium titanate), a titanium sulfate (such as titanium orthosulfate), and a titanium halide (such as titanium dichloride, titanium trichloride, etc.).

[0018] In the present invention, there is no particular restriction on the sources of the titanium-containing compound, the phosphorus-containing compound and the antimony-containing compound. They may be externally added titanium-containing compounds, phosphorus-containing compounds and antimony-containing compounds, or they may be non-externally added, as long as the weight content and weight ratio of the three elements of titanium, phosphorus and antimony in the obtained PBS resin composition are within the range defined in the present invention.

[0019] In the present invention, there is no particular restriction on the types of titanium-containing compounds, phosphorus-containing compounds and antimony-containing compounds. The compounds are not limited to the above-mentioned compounds, and any compound containing titanium, phosphorus or antimony in the molecular structure may be used.

[0020] Preferably, according to standard ISO 1133-1:2022, the melt index of the PBS resin composition at 190°C and 2.16kg is ≤35g / 10min, for example, it can be 35g / 10min, 30g / 10min, 25g / 10min, 20g / 10min, 15g / 10min, 10g / 10min, 5g / 10min or a range between any of the above values, more preferably, the melt index is ≤31g / 10min, more preferably, the melt index is ≤21g / 10min, and particularly preferably, the melt index is 3.5 to 10.5g / 10min.

[0021] Preferably, the absolute value of the b value of the PBS resin composition is ≤2, more preferably the absolute value of the b value is ≤1.5, more preferably the absolute value of the b value is ≤1, and particularly preferably the absolute value of the b value is ≤0.6.

[0022] In the present invention, yellowness is represented by the absolute value of b value and is tested using the CIE 1976 (L*a*b*) color system.

[0023] Preferably, the heat resistant temperature (HDT) of the PBS resin composition is ≥93°C, for example, it can be 93°C, 93.2°C, 93.4°C, 93.6°C, 93.8°C, 94°C, 94.2°C, 94.4°C, 94.6°C, 94.8°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C or a range between any of the above values; more preferably, the heat resistant temperature is ≥94°C, and more preferably, the heat resistant temperature is 96-100°C.

[0024] In the present invention, the heat resistance temperature is tested according to standard GB / T 1634.2-2019.

[0025] In a second aspect, the present invention provides a method for preparing the PBS resin composition according to the first aspect, the preparation method comprising the following steps:

[0026] S1: reacting succinic acid, 1,4-butanediol, a titanium-containing compound, a phosphorus-containing compound and an antimony-containing compound, and granulating to obtain the PBS resin composition.

[0027] Preferably, the reaction in step S1 comprises the following steps:

[0028] (1) mixing succinic acid, 1,4-butanediol, and a titanium-containing compound, and reacting them to obtain a first reactant;

[0029] (2) in the presence of a protective atmosphere, the first reactant obtained in step (1) undergoes a first-stage reaction, and then a phosphorus-containing compound and an antimony-containing compound are added to undergo a second-stage reaction to obtain a second reactant;

[0030] (3) reducing the pressure, continuing the reaction of the second reactant obtained in step (2), then filling with nitrogen, and granulating to obtain the PBS resin composition.

[0031] Preferably, the molar ratio of succinic acid to 1,4-butanediol in step (1) is 1:(1.1-1.5), for example, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5 or a range between any of the above values.

[0032] Preferably, in step (1), the added mass of the titanium-containing compound is 200-1700 ppm, based on the amount of the succinic acid, for example, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, 1500 ppm, 1600 ppm, 1700 ppm or a range between any of the above values.

[0033] Preferably, the reaction pressure in step (1) is 30-100 kPa, for example, 30 kPa, 50 kPa, 70 kPa, 80 kPa, 90 kPa, 100 kPa or any range between the above values; the reaction temperature is 180-250°C, for example, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C or any range between the above values; the reaction time is 1-5 h, for example, 1 h, 2 h, 3 h, 4 h, 5 h or any range between the above values.

[0034] In the present invention, the protective atmosphere in step (2) includes but is not limited to nitrogen.

[0035] In the present invention, based on the dosage of the succinic acid, the added mass of the phosphorus-containing compound is 10 to 850 ppm, for example, it can be 20 ppm, 40 ppm, 60 ppm, 80 ppm, 100 ppm, 120 ppm, 150 ppm, 160 ppm, 180 ppm, 200 ppm, 220 ppm, 250 ppm, 280 ppm, 300 ppm, 320 ppm, 350 ppm, 380 ppm, 400 ppm, 420 ppm, 450 ppm, 480 ppm, 500 ppm, 520 ppm, 550 ppm, 580 ppm, 600 ppm, 620 ppm, 650 ppm, 680 ppm, 700 ppm, 720 ppm, 750 ppm or a range between any of the above values.

[0036] In the present invention, based on the dosage of the succinic acid, the added mass of the antimony-containing compound is 15 to 570 ppm, for example, it can be 30 ppm, 40 ppm, 60 ppm, 80 ppm, 100 ppm, 120 ppm, 150 ppm, 160 ppm, 180 ppm, 200 ppm, 220 ppm, 250 ppm, 280 ppm, 300 ppm, 320 ppm, 350 ppm, 380 ppm, 400 ppm, 420 ppm, 450 ppm, 480 ppm, 500 ppm or a range between any of the above values.

[0037] Preferably, the added mass ratio of the phosphorus-containing compound to the titanium-containing compound is 1:(2-20), for example, it can be 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20 or a range between any of the above values.

[0038] Preferably, the added mass ratio of the antimony-containing compound to the titanium-containing compound is 1:(1-25.2), for example, it can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, 1:22, 1:24, 1:25 or a range between any of the above values, more preferably 1:(3-12).

[0039] Preferably, the temperature of the first-stage reaction in step (2) is 180-240°C, for example, it can be 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C or any range between the above values, and the reaction time is 2-5h, for example, it can be 2h, 3h, 4h, 5h or any range between the above values.

[0040] Preferably, the temperature of the second-stage reaction in step (2) is 180-240°C, for example, it can be 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C or any range between the above values; the time of the second-stage reaction is 10-30min, for example, it can be 10min, 15min, 20min, 25min, 30min or any range between the above values.

[0041] Preferably, the reaction pressure in step (3) is less than 200 Pa, for example, 180 Pa, 140 Pa, 100 Pa, 60 Pa, 30 Pa or any range between the above values.

[0042] Preferably, the reaction temperature in step (3) is 230-250°C, for example, 230°C, 235°C, 240°C, 245°C, 250°C or any range between the above values, and the reaction time is 3-6h, for example, 3h, 4h, 5h, 6h or any range between the above values.

[0043] It should be noted that the types and sources of the titanium-containing compounds, phosphorus-containing compounds and antimony-containing compounds involved in the second aspect have the same limited scope as those in the first aspect.

[0044] In a third aspect, the present invention provides a use of the PBS resin composition described in the first aspect in preparing degradable film bags, straws, and tableware.

[0045] Compared with the prior art, the present invention has at least the following beneficial effects:

[0046] The PBS resin composition provided by the invention contains titanium, phosphorus and antimony, and by controlling the weight ratio of titanium, phosphorus and antimony within a specific range, the PBS resin composition has low yellowness and excellent heat resistance. DETAILED DESCRIPTION

[0047] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0048] Unless otherwise specified, the sources of raw materials for the examples and comparative examples of the present invention are as follows:

[0049] Succinic acid-1: purity ≥99.9%, Shandong Landian Biotechnology Co., Ltd.;

[0050] Succinic acid-2: purity ≥99.8%, Shandong Feiyang Chemical Co., Ltd.;

[0051] 1,4-Butanediol: purity ≥99.5%, Wanhua Chemical (Yantai) Sales Co., Ltd.;

[0052] Butyl titanate: purity ≥99.0%, Tianjin Komiou Reagent;

[0053] Isopropyl titanate: purity ≥99.0%, Tianjin Komiou Reagent;

[0054] Triphenyl phosphate: purity ≥98.0%, Aladdin reagent;

[0055] Trimethyl phosphate: purity ≥98.0%, Aladdin reagent;

[0056] Antimony trioxide: purity ≥99.0%, Aladdin reagent;

[0057] Antimony acetate: purity ≥99.0%, Aladdin reagent.

[0058] In the present invention, the phosphorus content, titanium content and antimony content in the PBS resin composition are tested with reference to USEPA3052:1996 method, analyzed by ICP-OES, and measured according to the following procedure: 0.1g of the PBS resin composition is weighed, crushed, and 5mL of nitric acid is added to completely immerse the PBS resin composition, then 1.0mL of hydrogen peroxide is dropped into it for reaction for 2min, sealed in a microwave digestion tank and digested at 210°C for 3 hours, cooled to room temperature, filtered with a 0.45μm filter membrane, and diluted to 50mL with distilled water, and tested by ICP-OES, the instrument is a Spectro arcos FHS12 inductively coupled plasma emission spectrometer, AMETEK, USA.

[0059] Examples 1-14 and Comparative Examples 1-4

[0060] In Examples 1-14 and Comparative Examples 1-4, a PBS resin composition is provided, and the preparation method comprises the following steps:

[0061] (1) Succinic acid, 1,4-butanediol, and a titanium-containing compound are mixed and reacted at 50 kPa and 190° C. for 3 h to obtain a first reactant;

[0062] (2) introducing N2 into the first reactant obtained in step (1), reacting at 200°C for 3h, then adding a phosphorus-containing compound and an antimony-containing compound, and continuing the reaction at 200°C for 20min to obtain a second reactant;

[0063] (3) reducing the pressure of the system in step (2) to 100 Pa, reacting at 240° C. for 4 h, introducing nitrogen, and granulating to obtain the PBS resin composition. The added mass (unit: kg) of each raw material of the PBS composition and the mass content (unit: ppm) of phosphorus, titanium and antimony actually measured in the PBS composition are shown in Table 1-4.

[0064] Table 1

[0065]

[0066] Table 2

[0067]

[0068]

[0069] Table 3

[0070]

[0071] Table 4

[0072]

[0073]

[0074] The PBS resin compositions provided in the examples and comparative examples were subjected to performance tests, and the test methods were as follows:

[0075] (1) Melt index: tested according to ISO 1133-1:2022 at 190°C and 2.16 kg weight;

[0076] (2) b value: Lab value test is a color description method based on the Lab color space recommended by CIE (International Commission on Illumination). It converts color from three-dimensional space (chromaticity, brightness and saturation) to two-dimensional space (Lab value), thereby achieving a unified description of color. According to the standard CIE 1976 (L*a*b*) color system, a colorimeter is used to test the b value of the PBS composition under D65 light source, and the absolute value of the b value is recorded;

[0077] (3) Heat resistance: Heat resistance is expressed by heat deformation temperature HDT and is tested in accordance with standard GB / T1634.2-2019. Test conditions: 0.45 MPa, flat.

[0078] The performance test results are shown in Table 5.

[0079] Table 5

[0080]

[0081]

[0082] It can be seen from Table 5 that the PBS resin compositions provided in the embodiments of the present invention have lower yellowness and excellent heat resistance; the absolute value of the b value is ≤1.5, and the HDT is ≥93.2°C.

[0083] The heat resistance of the PBS resin composition provided in Comparative Example 1 is significantly worse; the yellowness of the PBS resin composition provided in Comparative Example 2 is high and the heat resistance is poor; the yellowness of the PBS resin composition provided in Comparative Example 3 is high and the heat resistance is poor. The melt index of the PBS resin composition provided in Comparative Example 4 is significantly increased and the heat resistance is significantly worse.

[0084] The applicant declares that the present invention illustrates the PBS resin composition and its preparation method and application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A PBS resin composition, characterized in that: The PBS resin composition comprises PBS resin, titanium element, phosphorus element and antimony element; In the PBS resin composition, the weight content of titanium element is 20-150 ppm, the weight content of phosphorus element is 2-50 ppm, and the weight content of antimony element is 1-100 ppm; In the PBS resin composition, the weight ratio of titanium element, phosphorus element and antimony element is (2-20):1:(0.5-10).

2. PBS resin composition according to claim 1, characterized in that, In the PBS resin composition, the weight content of titanium element is 30-130 ppm, the weight content of phosphorus element is 5-22 ppm, and the weight content of antimony element is 20-70 ppm.

3. PBS resin composition according to claim 1, characterized in that, In the PBS resin composition, the weight ratio of titanium element, phosphorus element and antimony element is (3-15):1:(1-8), and more preferably, the weight ratio of titanium element, phosphorus element and antimony element is (4-11.5):1:(2-6.5).

4. PBS resin composition according to claim 1, characterized in that, The source of the phosphorus element includes a phosphorus-containing compound, and the phosphorus-containing compound includes at least one of a phosphorus acid compound, a phosphorus oxide, a phosphorus salt compound, or a phosphorus ester compound; Preferably, the source of the antimony element includes an antimony-containing compound, and the antimony-containing compound includes at least one of antimony oxide, antimony sulfide, antimony hydroxide, antimony salt compound or antimony metal compound; Preferably, the source of the titanium element includes a titanium-containing compound, and the titanium-containing compound includes at least one of a titanium oxide, a titanium ester compound or a titanium salt compound.

5. PBS resin composition according to claim 1, characterized in that, The PBS resin composition has a melt index of ≤35 g / 10 min at 190° C. and 2.16 kg.

6. PBS resin composition according to claim 1, characterized in that, The absolute value of the b value of the PBS resin composition is ≤2; Preferably, the heat-resistant temperature of the PBS resin composition is ≥93°C.

7. A method for preparing a PBS resin composition as described in any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: S1: reacting succinic acid, 1,4-butanediol, a titanium-containing compound, a phosphorus-containing compound and an antimony-containing compound, and granulating to obtain the PBS resin composition.

8. The preparation method according to claim 7, characterized in that: The reaction in step S1 comprises the following steps: (1) mixing succinic acid, 1,4-butanediol, and a titanium-containing compound, and reacting them to obtain a first reactant; (2) in the presence of a protective atmosphere, subjecting the first reactant obtained in step (1) to a first-stage reaction, and then adding a phosphorus-containing compound and an antimony-containing compound to a second-stage reaction to obtain a second reactant; (3) reducing the pressure, continuing the reaction of the second reactant obtained in step (2), then filling with nitrogen, granulating, and obtaining the PBS resin composition.

9. The preparation method according to claim 8, characterized in that: The molar ratio of succinic acid to 1,4-butanediol in step (1) is 1:(1.1-1.5); Preferably, in step (1), the added mass of the titanium-containing compound is 200-1700 ppm based on the amount of the succinic acid used; Preferably, the reaction pressure in step (1) is 30-100 kPa, the reaction temperature is 180-250° C., and the reaction time is 1-5 h; Preferably, the added mass ratio of the phosphorus-containing compound to the titanium-containing compound is 1:(2-20); Preferably, the added mass ratio of the antimony-containing compound to the titanium-containing compound is 1:(1-25.2); Preferably, the temperature of the first stage reaction in step (2) is 180-240° C., and the first stage reaction time is 2-5 h; Preferably, the temperature of the second stage reaction in step (2) is 180-240° C., and the time of the second stage reaction is 10-30 min; Preferably, the reaction pressure in step (3) is less than 200 Pa; Preferably, the reaction temperature in step (3) is 230-250° C., and the reaction time is 3-6 h.

10. Use of the PBS resin composition according to any one of claims 1 to 6 in preparing degradable film bags, straws and tableware.

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